One of the challenges in the processing of advanced composite materials with 2D reinforcement is their extensive agglomeration in the matrix. 3D architecture of 2D graphene sheets into a Graphene Foam (GrF) assembly has emerged as an effective way to overcome agglomeration. The highly reticulated network of branches and nodes of GrF offers a seamless pathway for photon and electron conduction in the matrix along with improved mechanical properties. 3D GrF nano-filler is often fabricated by chemical vapor deposition (CVD) technique, which demands high energy, slow deposition rate, and restricting production to small scale. This work highlights freeze-drying (FD) technique to produce 3D graphene nanoplatelets (GNP) foam with a similar hierarchical structure to the CVD GrF. The FD technique using water as the main chemical in 3D GNP foam production is an added advantage. The flexibility of the FD in producing GNP foams of various pore size and morphology is elucidated. The simplicity with which one can engineer thermodynamic conditions to tailor the pore shape and morphology is presented here by altering the GNP solid loading and mold geometry. The FD 3D GNP foam is mechanically superior to CVD GrF as it exhibited 1280 times higher elastic modulus. However, thermal diffusivity of the FD GNP foam is almost 0.5 times the thermal diffusivity of the CVD GrF due to the defects in GNP particles and pore architecture. The versatility in GNP foam scalability and compatibility to form foam of other 1D and 2D material systems (e.g., carbon nanotubes, boron nitride nanotubes, and boron nitride nanoplatelets) brings a unique dimensionality to FD as an advanced engineering foam development process.

A cryo-system assisted extrusion 3D printing technique has been developed to fabricate Shape Memory Polymer Epoxy (SMPE) thermoset into a near-net shape. With a unique cryogenic sprayer assisted printing system, it is possible to 3D print "pure" thermoset polymer, otherwise which was limited to thermoplastic or highly functionalized co-polymeric thermoset systems. The temperature was maintained below 10oC during 3D printing, which enabled dimensionally accurate structures. Graphene Nanoplatelet (GNP) reinforced SMPE ink was synthesized to be compatible with cryo-assisted extrusion 3D printing of shape memory composites. The addition of a mere 0.1 wt.% GNP exhibited 15% faster shape recovery due to improved thermal conductivity. Also, GNP addition imparted a 30% improvement in the ultimate tensile strength and a 17% increase in 3D printed composites' elastic modulus. Dynamic mechanical testing showed that the addition of 0.1 wt.% GNP in SMPE increased the composite's storage modulus by 365% and loss tangent by 66% compared to pure 3D printed SMPE, indicating enhanced damping characteristics. This study is the first to demonstrate a non-existent 3D printing technology for “pure thermoset” polymers with and without conductive graphene, that has the potential to develop an energy-efficient actuation system, passive thermal sensors, and self-deployable communication system structures.

Shape memory polymer (SMP) epoxy composites have attracted significant attention due to their easy processing, lightweight nature, and ability to recover strain. However, their limited recovery rate and inferior mechanical properties have hindered their functional applications. This research explores the potential of three-dimensional (3D) graphene foam (GrF) as a highly efficient reinforcement for SMP epoxy composites. We demonstrated that the incorporation of a mere 0.13 wt.% GrF into mold-cast SMP epoxy leads to a 19% increase in the glass transition temperature (T_g). To elucidate the reinforcing mechanism, we fabricated and extensively analyzed composites with varying weight percentages of GrF. The GrF-based SMP epoxy composite exhibits a 57% increase in thermal conductivity, measuring 0.296 W mK⁻¹ at 70 °C, due to the interconnected 3D graphene network within the matrix. Notably, this composite also demonstrates remarkable electrical conductivity, making it suitable for dual-triggering applications. The GrF-SMP epoxy composite achieves a maximum shape recovery ratio and a significant 23% improvement in the recovery rate, effectively addressing the issue of slow recovery associated with SMPs. We investigated the effect of switching temperatures on the shape recovery rate. We identified the optimal triggering temperature to initiate shape recovery for epoxy SMP and GrF-epoxy SMP as thermal energy equivalent to T_g + 20 °C. Additionally, we fabricated a bird-shaped composite using GrF reinforcement, which showcases self-healing capabilities through the crack opening and closure and serves as a tangible demonstration of the transformative potential of the composite. These GrF-epoxy SMP composites, responsive to stimuli, hold immense promise for diverse applications, such as mechanical systems, wearable sensors, morphing wings, foldable robots, and antennas.